Vat-dyeing coloring-matter.



v with bromin. As initial materials for the vt-ives with substituted phenols or naphthol's atoms or atomic groups. Highly brmninated t UNITED STATES PA ENT OFFICE.

KARL ELBEL AND EDWARD WRAY, OF BiEIBRICI-I, GERMANY, ASSIGNORS TO THE FIRIM OF BALLE & COMPANY, AKTIENGESELLSCHAFT, 0F BIEBRICH, GERMANY:

VAT-DYEING COLORING-MATTER:

No Drawing.

Specification of Letters Patent.

Application filed March 14,

Patented Aug. 1, 1911. 1910. Serial No. 549,330. I

It is known that, by the condensation of alpha-reactive isatin derivatives with city derivatives of cycllc hydrocarbons as tor instance naphthol or anthrol or their derivatives, indigoid coloring matters are obtained. In this condensation thQ'PllBllOllO bodies rcact as if they contained. the group according to the following equation:

Compounds to be used for the condensation. and containing the hydroxyl group with a free ortho position, which contain substitucnts exwptiug such as are liable to hinder the formation of fast vat coloring matters (for instance free hydroxyh, or sulfo-, groups), yield indigoid. dyestuffs possessing some degree of fastness against v the action of all-ialis. But. notwithstanding this, only a few representatives of theabore named class of coloringmatters satisfy the high requirements to be met with in vat-- dyeing coloring matters'as regards general fastness. I

\Ve have now found that vat dyeiiiig col oring vmatters of considerably greater fastness can be obtained if the indigoid coloring matters be treated in a suitable manner bromination, the indigoid coloring matters prepared by condensing t.l1)l1t1-1St1tlll derivamaybe used, and also those which can be obtained from an alpha-isatin derivative capable of reaction by condensation with a compound of the aromatic series which, besides the hydroxyl group, contains no further substituent. In the latter case, it is necessary, in order to obtain satisfactorily fast products, to introduce into the molecule of the coloring matter larger amounts of bromin than when the initial productsare indigoid coloring matters in which a number of hydrogen atoms are substituted by other rat dyes can of course also be obtained by condens ng bromii'iated alpha-isatin derivai lives with phenols or naphtnols or substitution products of the same for instance those containing halogen atoms.

The following are examples of how this The mass is then stirred for three hours withou t the temperature being increased, and then the reaction mixture is allowed to stand for about six hours longer. It !is then poured into ice and a little sodium bisullit, and the 'precipitated coloring matteris filtered oil' and \Yell washedr In this manner a product is obtained which, in the vat, produces very pure blue shades on cotton.

Example II: In 1300 parts of sulfuric acid are suspended from 05 to 90' parts of bromin and then 43 parts of imlolealphanaphtholindigo obtained from alpha-i1a =h- .lndol-alphd-nlphtholhdlgo -,are introducedjnto the suspension. j The reaction miissis-then stirred for a few hours at ordi'n'a temperature, and isthen heated fo'r three ours; or thereabout, at about 50 "centigredeiI -Then the mass is diluted with ice water andfilteredand the 01121:? matter is .,wa'shed out. p u .'0n"cotton,,in the vat, blue tints of i-ema' able ifeshiess. Insteud of the coloring matters mentioned in'the foregoing examples, other indigoid coloring mattersmay be employed, and, in-

stead of bromi'n itself, sin may be used which saiecfapable of yieldingv bromin. Thebrominhtion can be carried out with chloro-sulfonic 'ac'id as well as withsulfuric acid and with dry bromin at ordinary temperature, or at a moderatelyhigh temperature, or at a still higher temperature by the use of neu-' tral dilution agents; I

It ippeu-s probable that pepbromids are first ormed and that these puss-into the substitution products.

the bggmingtion can be effected "new'productsto washing in part depends on the ofbiominatiomit-is necessiiry to introduce into the molecule of coloring matter quantifies of bromin in accordance with the nature of the initial product selected. Whatwe claimis: I I

1. The production of fast vat coloring matters consisting in treating with bromin the products obtainable by condensation of reactive alpha-isatin derivatives with oxy derivatives of cyclic hydrocarbons. r 2. The hereiii described process of producing a fast vat coloring matter consistin in treating with bromin the roduct obtaine by condensing dibrorno-alp a isatin-chlorid with alpha-naphthol.

3. As a new product the vat coloring matter consistin of the-brominated indol-al hana htholindigo being blue powder solub e in sufiuric acid with greenishbljue color, in hot nitrobenzene and in hot anilin with pure blue color, insoluble in water and alcohol yielding on alkaline reduction :1 yellow vat in which the textile fibers are dyed in bright blue shades.

In testimony whereof we have signed our names to this specification in the presence of two subscribing witnesses.

KARL ELBEL. I EDWARD WRAY.

. Witnesses:

HERMAN PLIsoHbE, MAXi-ZIESQHE.

It that the name ofthe Patent No; 999,439, uponibe tx fl Edward seventy; for an improvement in I *vten m' feblorin M tmm w Wor -its and pri i d.s the arm of me 4% i -t whereas said name should have the Patent Comctlon In Letters m1 dsyoj November, Ln, $1911.

[ cfl fi'onrpany, .and that the suid Letters Patent should be read with this cor-action tberein-ithit'thesame may confofln the record of the sstisfactoryfastness of the 3 .lndol-alphd-nlphtholhdlgo -,are introducedjnto the suspension. j The reaction miissis-then stirred for a few hours at ordi'n'a temperature, and isthen heated fo'r three ours; or thereabout, at about 50 "centigredeiI -Then the mass is diluted with ice water andfilteredand the 01121:? matter is .,wa'shed out. p u .'0n"cotton,,in the vat, blue tints of i-ema' able ifeshiess. Insteud of the coloring matters mentioned in'the foregoing examples, other indigoid coloring mattersmay be employed, and, in-

stead of bromi'n itself, sin may be used which saiecfapable of yieldingv bromin. Thebrominhtion can be carried out with chloro-sulfonic 'ac'id as well as withsulfuric acid and with dry bromin at ordinary temperature, or at a moderatelyhigh temperature, or at a still higher temperature by the use of neu-' tral dilution agents; I

It ippeu-s probable that pepbromids are first ormed and that these puss-into the substitution products.

the bggmingtion can be effected "new'productsto washing in part depends on the ofbiominatiomit-is necessiiry to introduce into the molecule of coloring matter quantifies of bromin in accordance with the nature of the initial product selected. Whatwe claimis: I I

1. The production of fast vat coloring matters consisting in treating with bromin the products obtainable by condensation of reactive alpha-isatin derivatives with oxy derivatives of cyclic hydrocarbons. r 2. The hereiii described process of producing a fast vat coloring matter consistin in treating with bromin the roduct obtaine by condensing dibrorno-alp a isatin-chlorid with alpha-naphthol.

3. As a new product the vat coloring matter consistin of the-brominated indol-al hana htholindigo being blue powder solub e in sufiuric acid with greenishbljue color, in hot nitrobenzene and in hot anilin with pure blue color, insoluble in water and alcohol yielding on alkaline reduction :1 yellow vat in which the textile fibers are dyed in bright blue shades.

In testimony whereof we have signed our names to this specification in the presence of two subscribing witnesses.

KARL ELBEL. I EDWARD WRAY.

. Witnesses:

HERMAN PLIsoHbE, MAXi-ZIESQHE.

It that the name ofthe Patent No; 999,439, uponibe tx fl Edward seventy; for an improvement in I *vten m' feblorin M tmm w Wor -its and pri i d.s the arm of me 4% i -t whereas said name should have the Patent Comctlon In Letters m1 dsyoj November, Ln, $1911.

[ cfl fi'onrpany, .and that the suid Letters Patent should be read with this mike-son tberein-ithit'thesame may confofln the record of the sstisfactoryfastness of the 3 Correction in Letters Patemt Nc. 999,439.

It is hereby certified that the name of the zstssignee in. ljetters Patent No. 999,439, August 1, 1911, upon the application of Ku.rl Elhel and Edward of BieHrichGermany, for an impro vement in Vat-Dyeing GbIoring-Matters, was efronepusly written and printed s the firm of RaHe& Company, Aktiengesellec haft, whereas said name should have been written lhdrfiziuted as be firm, ofxille c5? towany; Alctiengesellscitqft; and that the said Letters Patent should be read with this coi'i'eetion therein that'the same may conforln to the record of the casein 1 the Patent Oflie e.

Signed and this 7th day q November, A. 11, 1911,

E. B. MOORE,

[emu] Commissioner of Paten 

